EP0164135B1

EP0164135B1 - Magnetic recording medium

Info

Publication number: EP0164135B1
Application number: EP85107086A
Authority: EP
Inventors: Masahiro Saito; Akira Nakabayashi
Original assignee: C Uyemura and Co Ltd
Current assignee: C Uyemura and Co Ltd
Priority date: 1984-06-07
Filing date: 1985-06-07
Publication date: 1988-11-09
Also published as: US4724188A; EP0164135A3; EP0164135A2; JPS60261022A; DE3566179D1; JPH0248981B2

Description

Background of the invention

Field of the invention:

The present invention relates to a magnetic recording medium such as magnetic disc and magnetic drum. More particularly, it relates to a magnetic medium in which the non-magnetic layer is a nickel-copper-phosphorus layer containing 20 to 65% by weight of copper, which layer is formed by electroless plating.

Description of the prior art:

According to the conventional technology, magnetic recording media such as magnetic discs are produced by forming a non-magnetic layer on a non-magnetic substrate such as aluminum and then forming a magnetic layer thereon. The non-magnetic layer is usually a nickel-phosphorus (Ni-P) layer of comparatively high phosphorus content formed by electroless plating.
The Ni-P layer is deposited from an electroless nickel plating solution containing a hypophosphite as a reducing agent. It remains non-magnetic so long as it is kept at room temperature or it is left as it is after deposition; but it becomes magnetized when it is heated to more than about 200°C. This property causes a problem when the magnetic recording medium is manufactured. Although heating of the non-magnetic Ni-P layer up to 200°C, especially 100°C does not cause serious troubles, the non-magnetic Ni-P layer is exposed to high temperatures above 200°C when the magnetic layer is formed thereon by sputtering in the process of manufacturing the magnetic recording medium, resulting in magnetizing the non-magnetic Ni-P layer. The magnetization of the Ni-P layer adversely affects the performance of the magnetic recording medium.
A countermeasure worked out to solve this problem is to increase the content of phosphorus in the Ni-P layer to 10% and up, so that the magnetization is minimized. However, this does not bring about a satisfactory solution because the reduction of magnetization by the increase of phosphorus content is a matter of relativity. The Ni-P layer of high phosphorus content still becomes magnetized. Moreover, it is difficult to deposit the Ni-P layer of high phosphorus content in the stable manner.

Summary of the invention

It is an object of this invention to provide an improved magnetic recording medium in which a non-magnetic layer remains non-magnetic even when exposed to high temperatures.
As the result of extensive researches on a non-magnetic layer which remains non-magnetic even after heat treatment at high temperatures, the present inventors have found that a nickel-copper-phosphorus (Ni-Cu-P) layer containing 20 to 65% by weight of copper formed by electroless plating does not become magnetic even after heat treatment at 400°C for 1 hour, keeping the state it has when it is deposited from the plating solution. It was also found that the electroless Ni-Cu-P deposition layer affords a high-performance magnetic recording medium when a magnetic layer is formed thereon. The present invention had been completed based on these findings.
In the meantime, it is known that a Ni-Cu-P layer formed by electroless plating serves to reduce the formation of projections on the magnetic recording medium, as disclosed in Japanese Patent Laid-open No. 51024/1981. The Ni-Cu-P layer therein disclosed contains more than 65% by weight of copper (as in Example 1) or less than 1 % by weight (as in Example 2). In the former case, the electroless plating does not substantially proceed well because of the excessively high copper content. In any way, neither of the two cases suggests the concept of the present invention. It is the present inventors' new finding that a Ni-Cu-P non-magnetic layer containing 20 to 65% by weight of copper formed by electroless plating does not become magnetic even when it is heated above 200°C, particularly above 300°C, during sputtering which is carried out to form a magnetic layer thereon. Thus it affords a magnetic recording medium of high performance.
Therefore, the present invention provides a magnetic recording medium comprising a non-magnetic substrate, a non-magnetic layer formed on the substrate, and a magnetic layer formed on the non-magnetic layer, characterized in that the non-magnetic layer is a nickel-copper-phosphorus layer containing 20 to 65 wt% of copper, the layer being formed by electroless plating.
According to the magnetic recording medium of this invention, since the non-magnetic layer consists of the electroless Ni-Cu-P deposit containing 20 to 65% by weight of copper, the layer of the electroless Ni-Cu-P deposit does not become magnetized at all and remains non-magnetic state even when it is heated. Thus the magnetic recording medium of the invention exhibits good performance.
The above and other objects, features and advantages of the present invention will be more apparent from the following description.

Brief description of the drawing

Figure 1 is a sectional view of one embodiment of the magnetic recording medium according to this invention; and Figure 2 is a graph showing the relationship between the heat treatment temperature and the magnetization of the Ni-Cu-P layer of this invention and the Ni-P layers of different phosphorus content.

Detailed description of the invention

The magnetic recording medium of the present invention comprises, as shown in Figure 1, a non-magnetic substrate 10, a non-magnetic layer 20 formed on the substrate 10, and a magnetic layer 30 formed on the non-magnetic layer 20. Optionally, a protective layer 40 may be formed on the magnetic layer 30.
According to this invention, the non-magnetic layer 20 consists of an electroless Ni-Cu-P deposit. The Ni-Cu-P layer formed by electroless plating contains 20 to 65% by weight, preferably 30 to 55% by weight of copper. The non-magnetic layer that does not become magnetic when heated is obtained only when it contains copper as specified above. If the copper content is lower than 20% by weight, particularly lower than 10% by weight, the non-magnetic layer readily becomes magnetized, and therefore, the object of this invention cannot be achieved. On the other hand, if the copper content is higher than 65% by weight, the non-magnetic layer becomes readily oxidized and is so poor in adhesion and uniformity that it cannot be used for magnetic recording media. Incidentally, the non-magnetic layer may contain 4 to 10%, preferably 6 to 8% of phosphorus, and the remains are nickel.
The Ni-Cu-P layer as mentioned above is obtained by electroless plating from an electroless plating solution containing a water-soluble nickel salt such as NiS04. 6H₂0 and NiCI2. 6H₂0, a water-soluble copper salt such as CuSO₄ · 5H₂O and CuCl₂ · 2H₂O, a hypophosphite such as NaHPO₂ · H₂O, and a complexing agent. If necessary, the plating solution further contains a pH adjusting agent, a stabilizer, and other additives. The concentration of the water-soluble nickel salt may be 0.02 to 0.2 mol/liter; the concentration of the water-soluble copper salt may be 0.002 to 0.08 mol/liter; the molar ratio of nickel ion to copper ion may be 1/0.1 to 1/0.4, particularly 1/0.2 to 1/0.35; and the concentration of hypophosphite may be 0.1 to 0.5 mol/liter, if the resulting Ni-Cu-P layer is to contain 20 to 65% of copper and 4 to 10% of phosphorus.
Preferred examples of the complexing agent include (1) acetic acid, lactic acid, and other organic acids and their salts in which the coordinating atom is oxygen, (2) thioglycolic acid, cysteine and other compounds in which the coordinating atom is sulfur, and (3) ammonia, glycine, ethylene-diamine and other compounds in which the coordinating atom is nitrogen. The concentration (in mol) of the complexing agent may be equal to or higher than the concentration (in mol) of the total metal salts. The plating solution may have pH 8 to 12, and the plating temperature may be 40 to 90°C.
According to this invention, the thickness of the Ni-Cu-P layer may be properly selected; but usually it is 0.1 to 50 pm, preferably 10 to 30 pm.
In principle, the layer of ternary alloy (Ni-Cu-P) is formed by electroless plating from a plating solution containing the three elements. In actual, however, it is difficult to produce the layer of uniform composition (across thickness) and desired composition, because the rate of deposition decreases and the concentration of metal ions in the solution greatly fluctuates (particularly the concentration of copper ions decreases suddenly) as the plating proceeds. To cope with this problem, it is necessary to replenish nickel ions, copper ions, and reducing agent which are consumed as the plating proceeds and to add a pH adjusting agent that compensates the decreased pH of the plating solution.
The present inventors found that the replenishment of copper ions causes trouble. When copper ions are added while the plating it proceeding, the concentration of copper ions temporarily rises near the point of addition. The locally concentrated solution instantaneously forms a copper-rich surface on the substrate being plated, with the result that the plating reaction stops because copper is very poor in catalytic activity. In contrast, the replenishment of nickel ions does not inhibit the process of plating because nickel has high h catalytic activity and the surface of metallic nickel has the autocatalytic action.
The present inventors investigated further the method for using the Ni-Cu-P plating solution continuously by replenishment. As the result, it was found that this can be achieved by replenishing a mixture of a copper ion solution and a nickel ion solution when copper ions are to be replenished. Copper deposits together with nickel on the substrate even though the concentration of copper ions locally increases, and the nickel which has deposited helps the smooth plating on account of its autocatalytic action.
The above-mentioned finding suggests that it is preferable to replenish a mixture of copper ion solution and nickel ion solution if the electroless Ni-Cu-P plating is to be performed continuously. It is further preferable to add a complexing agent to the mixture. It effectively prevents copper hydroxide from precipitating when the mixture is added. The amount of the complexing agent is 1/20 mol to 1 mol for 1 mol of the total amount of nickel ions and copper ions. Where no complexing agent is added, the concentration of copper ions in the mixture should be lower than 20 g/liter so that the precipitation of copper hydroxide is prevented. If copper ions alone are added in high concentrations to the plating solution, copper hydroxide might precipitate, decomposing the plating solution.
The reducing agent and the pH adjusting agent may be added individually; but for stable, continuous use of the plating solution, it is preferable to mix them together prior to replenishment. The stabilizer may be added together with the reducing agent, the pH adjusting agent, or a mixture thereof.
The above-mentioned replenishers should be added according to the amount of each component which has been consumed or which is short, after the determination of the concentration of each component in the plating solution. In practice, it is not necessary to determine the concentration of all the components. Since the consumption of the reducing agent and the decrease of the pH value are approximately proportional to the amount of metal ions consumed, the amount of the reducing agent and pH adjusting agent to be replenished can be determined according to the concentration of metal ions (nickel ions and copper ions) in the plating solution. The replenishment may be performed continuously or intermittently. The replenishment should be made before the consumption of nickel ions reaches 1 g/liter, preferably 0.5 g/liter, so that stable electroless plating is carried out with a minimum of fluctuation in depositing rate and layer composition.
The non-magnetic substrate on which the non-magnetic Ni-Cu-P layer by electroless deposition is formed can be any known one. Examples of the substrate include non-magnetic metals such as aluminum, aluminum alloys, copper, copper alloys (e.g., brass, phosphor bronze), titanium, glasses, and plastics such as polyesters, polyamides, polycarbonates, ABS resin. When the Ni-Cu-P layer is formed on the substrate, the substrate may be pre-treated by the well-known method depending on the type of the substrate. For example, an aluminum substrate may be subjected to the following pretreatment, i.e.

(1) cleaning with an organic solvent and then by an alkaline cleaner,
(2) etching with a sodium hydroxide solution,
(3) acid dipping,
(4) zinc immersion dipping, and
(5) copper strike plating.

To a glass substrate and a plastic substrate, the pretreatment such as chemical etching, sensitizing and activating process may be carried out before the Ni-Cu-P electroless plating.
After the completion of the Ni-Cu-P electroless plating, the Ni-Cu-P layer may preferably be subjected to lapping and/or polishing so that the surface of Ni-Cu-P layer becomes smooth and even.
On the Ni-Cu-P layer, the magnetic layer is formed by the well-known method. Examples of the magnetic layer are y-Fe₂0₃ layer, Co-Ni layer, Co-Cr layer; Co-P layer, Co-Ni-P layer. The layer may usually be formed by vapor deposition method including sputtering, electroless plating method, electroplating method or coating method depending on the type of the magnetic layer to be formed. In this case, since the non-magnetic Ni-Cu-P layer contains 20 to 65% by weight of copper, it does not become magnetized at all even when it is heated above 200°C. Owing to this characteristic property, the Ni-Cu-P layer can be subjected to vapor deposition such as sputtering which is carried out in an atmosphere at 200°C and up, or still higher than 300°C in order to form magnetic layer without any troubles on magnetization.
Therefore, in the present invention, the vapor deposition method such as sputtering can usefully be employed for the formation of the magnetic layer, and y-Fe₂0₃ layer, Co-Ni layer, Co-Cr layer or the like can be effectively formed as a magnetic layer by sputtering. The thickness of the magnetic layer is not limited, and usually in the range of 10 nm (100 A) to 1 urn.
The magnetic layer may preferably be covered with the protective layer. It can be any known one such as inorganic layers including Si0₂, carbon, Cr-C, rodium, and organic layers. In the formation of the protective layer, vapor deposition method such as sputtering which is carried out in an atmosphere at 200°C or more can also be employed, and Si0₂ layer, carbon layer, Cr-C layer or the like can effectively be formed by sputtering. The thickness of the protective layer is not limited, and usually in the range of 0.05 to 0.5 pm.
As mentioned above, the magnetic recording medium of this invention has the electroless Ni-Cu-P deposition layer containing 20 to 65% by weight of copper. This layer does not become magnetic at all and remains non-magnetic even when it is heated. Thus the magnetic recording medium of this invention exhibits good performance.
The invention is now described in more detail with reference to the following examples.

Example 1

A copper plate which had been pretreated in the usual way was dipped in an electroless plating solution of the following composition to form a 10 (..1m thick Ni-Cu-P layer thereon. The resulting layer was found to be composed of Ni 46%, Cu 49% and P 5%.
The resulting layer was subjected to heat treatment for 1 hour at different temperatures.
For comparison, Ni-P layers each containing 8%, 9% and 13% of phosphorus were prepared by electroless plating, and they were subjected to heat treatment to investigate their magnetization in the same manner as above. The results are shown in Figure 2 attached hereto. The curve A in the graph represents the Ni-Cu-P layer of this invention, and the curves B, C, and D represent the Ni-P layers each containing 8%, 9%, and 13% of phosphorus, respectively. The results indicate that the Ni-Cu-P layer according to this invention is not magnetized at all even after a heat treatment at 400°C for 1 hour.
On the other hand, when the Ni-Cu-P layer contains less than 20% of copper, it is magnetized by heat treatment at 300°C. The degree of magnetization was almost equal to the Ni-P layer containing 13% of phosphorus. The layer containing copper in excess of 65% is excessively oxidized by heat treatment, and therefore it cannot be used for the magnetic recording medium.

Example 2

A copper plate measuring 1 dm² was continuously subjected to nickel-copper electroless plating with an initial plating solution and replenishing solutions each having the following compositions.
The volume of the plating solution was kept at 1 liter, and the replenishment was made as follows during the plating. The content of nickel and copper in the solution was determined every 30 minutes, and 10 ml of replenishing solution A was added for 1 g of nickel ions which had been consumed and 10 ml of replenishing solution B was added for 0.5 g of copper ions which had been consumed. The replenishing solutions A and B were mixed prior to addition. The consumption of the reducing agent was compensated by adding the replenishing solution C. The concentration of each component in the replenishing solution C is so established that the initial level is recovered when 10 ml of the solution is added to fill up 1 g of both nickel and copper which have been consumed. The decreased pH of the solution is corrected by adding the replenishing solution D, which is prepared such that it can be added in the same amount as the replenishing solution C.
During the electroless plating with occasional replenishment as mentioned above, the rate of plating, the stability of the solution, and the composition of the layer were examined each time when the deposit reached a prescribed amount. The results are shown in Table 1.
For comparison, plating was continued without replenishment. The results are also shown in Table 1.
The Ni-Cu-P layer obtained in this example was not magnetized at all by heat treatment at 400°C for 1 hour.

Claims

1. A magnetic recording medium comprising a non-magnetic substrate, a non-magnetic nickel-copper-phosphorus layer formed on the substrate, and a magnetic layer formed on the non-magnetic layer, characterized in that the non-magnetic nickel-copper-phosphorus layer contains 20 to 65% by weight of copper, the layer being formed by electroless plating.

2. The medium according to claim 1, wherein the copper content of the nickel-copper-phosphorus layer is in the range of 30 to 55% by weight.

3. The medium according to claim 1, wherein the phosphorus content of the nickel-copper-phosphorus layer is in the range of 4 to 10% by weight.

4. The medium according to claim 1, wherein the magnetic layer is formed by a vapor deposition method which is carried out in an atmosphere at 200°C or more.

5. The medium according to claim 4, wherein the vapor deposition is sputtering.

6. The medium according to claim 1, wherein a protective layer is formed on the magnetic layer.

7. The medium according to claim 1, wherein the protective layer is formed by a vapor deposition method.

8. A process for manufacturing a magnetic recording medium comprising:

-forming a nickel-copper-phosphorus layer containing 20 to 65% by weight of copper on a non-magnetic substrate by electroless plating from an electroless plating solution containing nickel ions, copper ions, a hypophosphite and a complexing agent and

-forming a magnetic layer on the nickel-copper-phosphorus layer.

9. The process according to claim 8, wherein the copper content of the nickel-copper-phosphorus layer is in the range of 30 to 55% by weight.

10. The process according to claim 8, wherein the phosphorus content of the nickel-copper-phosphorus layer is in the range of 4 to 10% by weight.

11. The process according to claim 8, wherein the magnetic layer is formed by a vapor deposition method which is carried out in an atmosphere at 200°C or more.

12. The process according to claim 11, wherein the vapor deposition is sputtering.

13. The process according to claim 8, wherein a protective layer is formed on the magnetic layer.

14. The process according to claim 13, wherein the protective layer is formed by a vapor deposition method.